EPR and SQUID magnetometry study of Cu 2 FeSnS 4 (stannite) and Cu 2 ZnSnS 4 (kesterite)

Bernardini, G. P.; Borrini, Daniele; Caneschi, Andrea; Benedetto, Francesco Di; Gatteschi, Dante; Ristori, Sandra; Romanelli, Marco

doi:10.1007/s002690000086

Cited by 82 publications

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“…40 Partially substituting (doping) Cu 2 M x Zn 1−x SnS 4 nanorods (M = Mn 2+ , Co 2+ , Ni 2+ ) with a wurtzite crystal structure (P6 3 mc) could lead to additional and interesting magnetic properties. 16,57 Simple considerations predict that doping and even complete solid solutions are possible over the whole Cu 2 M x Zn 1−x SnS 4 composition range (0 ≤ x ≤ 1). Across these series, available lattice parameters differ little, by less than 1%, as do ionic radii for the four-coordinate Zn 2+ , Mn 2+ , Co 2+ , and Ni 2+ , by less than 10% (Table 1).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…This Cu 2+ signal has been seen before in kesterite CZTS nanocrystals and indicates that there may be a mixture of Cu + and Cu 2+ defects in our samples. 57,100,102 To confirm the oxidation states of the metals and sulfur in the cobalt doped CZTS nanocrystals, we employed X-ray photoelectron spectroscopy (XPS), as shown in Figure 7. Cu 2p 1/2 and 2p 3/2 peaks at 951.9 and 932.1 eV are indicative of Cu(I) with a splitting of 19.8 eV.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Cu₂ZnSnS₄ Nanorods Doped with Tetrahedral, High Spin Transition Metal Ions: Mn²⁺, Co²⁺, and Ni²⁺

Thompson

Blakeney²,

Cady³

et al. 2016

Chem. Mater.

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Because of its useful optoelectronic properties and the relative abundance of its elements, the quaternary semiconductor Cu 2 ZnSnS 4 (CZTS) has garnered considerable interest in recent years. In this work, we dope divalent, high spin transition metal ions (M 2+ = Mn 2+ , Co 2+ , Ni 2+ ) into the tetrahedral Zn 2+ sites of wurtzite CZTS nanorods. The resulting Cu 2 M x Zn 1−x SnS 4 (CMTS) nanocrystals retain the hexagonal crystalline structure, elongated morphology, and broad visible light absorption profile of the undoped CZTS nanorods. Electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), and infrared (IR) spectroscopy help corroborate the composition and local ion environment of the doped nanocrystals. EPR shows that, similarly to Mn x Cd 1−x Se, washing Cu 2 Mn x Zn 1−x SnS 4 nanocrystals with trioctylphosphine oxide (TOPO) is an efficient way to remove excess Mn 2+ ions from the particle surface. XPS and IR of as-isolated and thiol-washed samples show that, in contrast to binary chalcogenides, Cu 2 Mn x Zn 1−x SnS 4 nanocrystals aggregate not through dichalcogenide bonds, but through excess metal ions cross-linking the sulfur-rich surfaces of neighboring particles. Our results may help in expanding the synthetic applicability of CZTS and CMTS materials beyond photovoltaics and into the fields of spintronics and magnetic data storage.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Cu₂ZnSnS₄ Nanorods Doped with Tetrahedral, High Spin Transition Metal Ions: Mn²⁺, Co²⁺, and Ni²⁺

Thompson

Blakeney²,

Cady³

et al. 2016

Chem. Mater.

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“…EDX quantitative analysis confirmed these secondary phases as CuS. Previous growth of CZTS by this method required annealing for a total of 16 days; 36,37 it has been shown that CZTS polycrystals can be successfully grown in 24 h. X-ray powder diffraction was performed on the samples to confirm the CZTS structure and explore the possible identification of additional phases. Low temperature PL spectroscopy was performed with the samples mounted under vacuum in a closed cycle helium cryostat.…”

Section: Sample Preparation and Measurementsmentioning

confidence: 99%

Luminescence of Cu2ZnSnS4 polycrystals described by the fluctuating potential model

Halliday

Claridge

Goodman

et al. 2013

Journal of Applied Physics

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The growth of Cu2ZnSnS4 (CZTS) polycrystals from solid state reaction over a range of compositions, including the regions which produce the highest efficiency photovoltaic devices, is reported. X-ray measurements confirm the growth of crystalline CZTS. Temperature and intensity dependent photoluminescence (PL) measurements show an increase in the energy of the main CZTS luminescence peak with both increasing laser power and increasing temperature. Analysis of the PL peak positions and intensity behavior demonstrates that the results are consistent with the model of fluctuating potentials. This confirms that the polycrystals are heavily doped with the presence of a large concentration of intrinsic defects. The behavior of the main luminescence feature is shown to be qualitatively similar over a broad range of compositions although the nature and amount of secondary phases vary significantly. The implications for thin-film photovoltaic devices are discussed.

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“…EPR measurements were performed on a Bruker 200D spectrometer equipped with ST100/700 variable-temperature assembly interfaced with Stelar software to an IBM PC computer. EPR data were collected on powders, dispersed in paraffin wax in pure amorphous silica capillaries, as reported in Bernardini et al (2000), and the spectra were registered at the X band in the temperature range from 130 to 298 K. The g-values were refined with reference to the external standard DPPH [2,2-di(4-tert-octylphenyl)-1-picrylhydrazyl] value (g = 2.0037).…”

Section: Analytical Proceduresmentioning

confidence: 99%

“…Whereas the compositional characterization has been performed for all samples, EPR and direct magnetic measurements have been used only on selected samples. As proposed by Calas (1988) and Bernardini et al (2000), in fact, determination of the values of the components of the magnetic tensors, g, hyperfine A and zero-field splitting, can give a significant contribution to knowledge of the structure of the paramagnetic site and, in particular, to the solution of problems related to the valence states and to the site occupancies of Cu 2+ and Fe 2+ .…”

Section: Introductionmentioning

confidence: 99%

Crystal Chemistry of Tetrahedrite Solid-Solution: Epr and Magnetic Investigations

Benedetto

Bernardini

Borrini

et al. 2002

The Canadian Mineralogist

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One hundred and thirty samples from the collection of the Natural History Museum in Florence, labeled as tetrahedrite, have been extensively studied by means of SEM, XRD, EPMA, DTA, EPR and SQUID techniques. Wide-ranging substitutions, confirmed by compositional data, play a fundamental role in the thermal behavior, "stabilizing" natural tetrahedrite with respect to the synthetic equivalent. In order to determine the valence state and site occupancies of Cu and Fe, electron paramagnetic resonance (EPR) and magnetic measurements were performed on selected samples of natural tetrahedrite. EPR measurements were performed down to 130 K, and magnetic susceptibility measurements, in the range 2-300 K. EPR magnetic parameters were determined on the basis of spectral simulations. The behaviour of --1 versus temperature was interpreted by means of Heisenberg's model, thus yielding values for the Curie and Weiss constants. All samples are characterized by the presence of small amounts of Cu 2+ and Fe 2+ ; Fe 3+ was detected only in metal-deficient samples. Both Cu and Fe occupy the tetrahedral site; whereas in some samples the former appears aggregated in dimers, the latter is randomly distributed over the lattice. The results of the study confirm the crystal-chemical formula of the tetrahedrite samples investigated.Keywords: tetrahedrite solid-solution, compositional data, thermal behavior, electron paramagnetic resonance, magnetic susceptibility, crystal chemistry, cupric ion. SOMMAIRENous avons caractérisé cent-trente échantillons appelés tétraédrite dans la collection du Musée d'Histoire Naturelle à Florence par microscopie électronique par balayage, diffraction X, analyse par microsonde électronique, analyse thermique différentielle, résonance paramagnétique des électrons, et la technique SQUID. Des substitutions d'étendue importante, confirmées par données chimiques, exercent un rôle fondamental dans le comportement thermique, "stabilisant" la tétraédrite naturelle par rapport à l'équivalent synthétique. Afin de déterminer la valence et la position de Cu et Fe, nous avons déterminé la résonance paramagnétique des électrons (RPE) d'échantillons naturels choisis jusqu'à 130 K, et les propriétés magnétiques sur l'intervalle 2-300 K. Les paramètres magnétiques des spectres RPE ont été déterminés par simulation. Le comportement de --1 en fonction de la température a été interpreté au moyen du modèle de Heisenberg, menant ainsi à une évaluation des constantes de Curie et de Weiss. Tous les échantillons contiennent de faibles quantités de Cu 2+ et de Fe 2+ . En revanche, on a décelé le Fe 3+ seulement dans les échantillons déficitaires en métaux. Le Cu et le Fe occupent le site tétraédrique. Tandis que le Cu semble agencé en dimères, le Fe serait plutôt distribué de façon aléatoire dans le réseau. Les résultats de notre étude confirment la formule cristallochimique des échantillons de tétraédrite étudiés. (Traduit par la Rédaction)Mots-clés: solution solide de la tétraédrite, données sur la composition, comportemen...

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EPR and SQUID magnetometry study of Cu 2 FeSnS 4 (stannite) and Cu 2 ZnSnS 4 (kesterite)

Cited by 82 publications

References 0 publications

Cu₂ZnSnS₄ Nanorods Doped with Tetrahedral, High Spin Transition Metal Ions: Mn²⁺, Co²⁺, and Ni²⁺

Cu₂ZnSnS₄ Nanorods Doped with Tetrahedral, High Spin Transition Metal Ions: Mn²⁺, Co²⁺, and Ni²⁺

Luminescence of Cu2ZnSnS4 polycrystals described by the fluctuating potential model

Crystal Chemistry of Tetrahedrite Solid-Solution: Epr and Magnetic Investigations

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EPR and SQUID magnetometry study of Cu 2 FeSnS 4 (stannite) and Cu 2 ZnSnS 4 (kesterite)

Cited by 82 publications

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Cu2ZnSnS4 Nanorods Doped with Tetrahedral, High Spin Transition Metal Ions: Mn2+, Co2+, and Ni2+

Cu2ZnSnS4 Nanorods Doped with Tetrahedral, High Spin Transition Metal Ions: Mn2+, Co2+, and Ni2+

Luminescence of Cu2ZnSnS4 polycrystals described by the fluctuating potential model

Crystal Chemistry of Tetrahedrite Solid-Solution: Epr and Magnetic Investigations

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Product

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Cu₂ZnSnS₄ Nanorods Doped with Tetrahedral, High Spin Transition Metal Ions: Mn²⁺, Co²⁺, and Ni²⁺

Cu₂ZnSnS₄ Nanorods Doped with Tetrahedral, High Spin Transition Metal Ions: Mn²⁺, Co²⁺, and Ni²⁺